To meet the high temperature and anti-reveling properties required in open-graded friction course, high content polymer modified asphalt (HCPMA) is gradually widely used in China, but the rheological, chemical and aging characteristic is not clear yet. In this paper, HCPMA with different SBS content and different base asphalt are prepared, and Pressure Aging Vessel (PAV) aging was conducted to simulate the long-term aging condition. The chemical and rheological evaluation of HCPMA before and after aging were tracked with Fourier transform infrared, gel permeation chromatography test, dynamic shear oscillatory test, master curve and multiple stress creep and recovery test. The results show that firstly, the aging of HCPMA is combined with hardening of asphalt and degradation of Styrene–butadiene–styrene (SBS) polymer. Furthermore, the addition of high content of SBS polymer can reduce the formation of carbonyl, but the degradation rate of SBS polymer is not related to the content of SBS or the type of base asphalt. Besides, HCPMA with a higher SBS content will have better rheological properties, but in consideration of economy, 9% is optimum dosage. At last, HCPMA prepared with Esso asphalt as base binder exhibits better rheological properties than HCPMA prepared with SK asphalt. However, the rheology difference reduces with the increase of SBS content and after PAV aging.